US922766A - Anhydrid of acyl salicylic acid. - Google Patents

Anhydrid of acyl salicylic acid. Download PDF

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Publication number
US922766A
US922766A US39999107A US1907399991A US922766A US 922766 A US922766 A US 922766A US 39999107 A US39999107 A US 39999107A US 1907399991 A US1907399991 A US 1907399991A US 922766 A US922766 A US 922766A
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salicylic acid
anhydrid
acyl
acid
soluble
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US39999107A
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Fritz Hofmann
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Bayer AG
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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C37/00Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
    • C07C37/01Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis
    • C07C37/055Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis the substituted group being bound to oxygen, e.g. ether group

Definitions

  • This invention relates to the manufacture and production of the hitherto unknown anhydrids of acyl-salicylic acids having most probably the following general formula:
  • the process for producing the new compounds consists in treating acyl-sahcyhc acids with phosgen in the presence of tertiary bases; 6. g pyridin.
  • the new products are white neutral compounds which do not give with ferric chlor d the violet coloration characteristic of sallcylic
  • the new compound forms white crystals melting at 82 to 83 C. and after repeated crystallization from alcohol at 85 C. It is tasteless and of neutral reaction, soluble with difficulty in ether and scarcely soluble in water, soluble in hot alcohol and easily soluble in acetone. On boiling it with an excess of caustic soda lye it is decomposed, salicylic acid being formed.
  • acyl salicylic acids obtainable by the action of phosgen and pyridin upon acyl salicylic acids which are White crystalline neutral com ounds soluble in hot alcoholfscarcely 'solu l'e-in water and do not give the violet coloration with ferric chlorid; which by heating with caustic alkalies are decom osed salicylic acid being formed and eXhi iting valuable therapeutic properties, substantially as hereinbefore described.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)

Description

FRITZ HOFMANN, OF ELBERFELD, GERMANY, ASSIGNOR TO FARBENFABRIKEN VORM. FRIEDR. BAYER & 00., OF ELBEBFELD', GERMANY, A CORPORATION OF GERMANY.
nnirn ,sras m ANHYDRID OF AGYL SALICYLIC ACID.
Specification of Letters-Patent. Patented May 25, 190% Application. filed Gctcbcr 31, 1907. Serial No. 399,991
and stirred. The reaction begins at once, carbonic acid being evolved and pyridin hydrochloridbeing precipitated. When the re To all whom it may concern:
Be it known that I, FRITZ HOFMANN, doctor of philosophy, chemist, citizen of the German Empire, residing at Elberfeld, Ger many, Kingdom of Prussia, have invented new and useful Improvements in Anhydrids of Acyl Salicylic Acids, of which the following is a specification.
This invention relates to the manufacture and production of the hitherto unknown anhydrids of acyl-salicylic acids having most probably the following general formula:
acid are added and the mixtureis well agitated in a separating funnel; The aqueous layer containing the pyridin hydrochlorid is separated from the benzene solution and the latter is water bath and the residue is extracted with 500 parts of warm ether (free from alcohol action is complete ice and dilute'hydrochloric I dried over granular chlorid ot calcium; the benzene is then distilled of? m vacuo on the /OR and water). On cooling the new anhydrid 7 x of acetyl salicylic acid having probably the formula: o.coori, C5H4\ a 4 0R oo (R meaning an acyl radical). v
These new products are valuable theraneutic compounds. They are tasteless and non-irritant and surpass in this respect even the acetyl salicylic acid frequently administercd as a substitute for salicylic acid. Acetyl salicylic acid has a marked acid taste fOnOWmg formula:
crystallizcs'h'om the ether. It is filtered oil and dried at from to C. lts formawhich is disag eeable to many patients and l (a H o.cocs., furthermore it may produce unpleasant re- \COOH a sults in case of abnormal sensitiveness oi the -n mucous membranes of the stomach. The n/ 5 oooon ococn8 new compounds do not suffer from these disadvantages and have proved to be valuable remedies for influenza, rheumatic or other diseases in which salicylic acid is administered. They are to be prescribed or taken in similar doses as sodium salicylate or acetyl salicylic acid.
The process for producing the new compounds consists in treating acyl-sahcyhc acids with phosgen in the presence of tertiary bases; 6. g pyridin.
The new products are white neutral compounds which do not give with ferric chlor d the violet coloration characteristic of sallcylic The new compound forms white crystals melting at 82 to 83 C. and after repeated crystallization from alcohol at 85 C. It is tasteless and of neutral reaction, soluble with difficulty in ether and scarcely soluble in water, soluble in hot alcohol and easily soluble in acetone. On boiling it with an excess of caustic soda lye it is decomposed, salicylic acid being formed.
The other anhydrids of acyl salicylic acids are )roduced in an analogous manner.
The anhydrid of carboxethyl salicylic acid acid. They are soluble in hot alcoholand o6H., z: scarcely soluble in water. 011 boiling the anhydrids for some time with pausticdalianes d al'c ic aci eing ocooo u they are decompose s 1 y melts at M C. I
formed.
In order to illustrate my inventionl give the/following example, parts being by weight: 158 parts of pyridin are added toa solution of 360 parts of acetyl salicylic acid in 500 parts of benzene, and a solution of 99 narts of phosgen in 500 parts of benzene is then added to this mixture while 1t 18 cooled The anhydrid of benzoylsalicylic acid oooon O6H4 r 5 co tion tal ies probably place according to the melts at 114-116 .C.
Having now described my invention and in what manner the same is to be performed, what claim as new and desire to LettersvPatent is y f1. Theherein-described new anhydrids, of
acyl salicylic acids obtainable by the action of phosgen and pyridin upon acyl salicylic acids which are White crystalline neutral com ounds soluble in hot alcoholfscarcely 'solu l'e-in water and do not give the violet coloration with ferric chlorid; which by heating with caustic alkalies are decom osed salicylic acid being formed and eXhi iting valuable therapeutic properties, substantially as hereinbefore described.
secure by 2. ,The herein-described new'anhyd rid" of acetyl salicylic acidhaving probably the above formula, obtainable bylthe action of phosgen and pyridin' upon 'acet'yl'salicylic acid, and being a white crystallinef'neutral compound melting at 85 C. after rec stalllZMZlOIlfIOIIl alcohol, being easily solu lein acetone, soluble in hot alcohol, soluble with difliculty in ether and being scarcely soluble in water and not givin the violet coloration with ferric ,chlorid, sa icylic acid being relye; and exhibiting valuable therapeutic properties, substantially as hereinbefore de scri ed.
In testimony whereof I have hereunto set my hand in the presence of two subscribing witnesses. FRITZ -HOFMANN. [L. s.]- Witnesses: 1
. OTTO KoNie, 7
WM. WASHINGTON BRUNSWICK.
7 generated by heating it with caustic soda
US39999107A 1907-10-31 1907-10-31 Anhydrid of acyl salicylic acid. Expired - Lifetime US922766A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2990328A (en) * 1958-04-18 1961-06-27 Upjohn Co Stable therapeutic compositions containing acetylsalicylic acid-anhydride
US3026350A (en) * 1959-06-22 1962-03-20 Warolin Christian Jean-Marie Process for preparing acetylsalicylic acid anhydride

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2990328A (en) * 1958-04-18 1961-06-27 Upjohn Co Stable therapeutic compositions containing acetylsalicylic acid-anhydride
US3026350A (en) * 1959-06-22 1962-03-20 Warolin Christian Jean-Marie Process for preparing acetylsalicylic acid anhydride

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